Method of producing substituted guanidine and biguanide salts



.,stituted guanidine and b'iguanide salts correoi' hydrogen and the radical ethylheml. n-octvl, iso-octyl, nonyl; decyl, do-

?a tentedJune 6,1944 1 UNITED- STATE s PATENT OFFICE 7 assoss METHOD OF rnonuomc SUBSTITUTED GUANIDINEANDBIGUANIDE SALTS Walter P. Erlcks, Stamford, Oonm, assignor to American a corporation of Cyanamld Company, New York, N. Y.,

Maine No Drawing. Application March}, 1942.

. Serial No. 433,298

3 Claims. (Cl. 260-564) The present invention relatesto the production ofguanidine and biguanide derivativesand more particularly to a method of producing sub- I spending to the formula iour carbon atoms chosen from the group con .sisting of alkyl and alkoxyalkyl radicals, R1 is a hydronalkyl radical, R: is a member of the moup consisting of hydrogen and a hydroxyalkyl radicalRsisamembei-oithesroupconsisting fl-H n-z r-n defined above. and x is a salt-- as R is as forming acid.

I have folmd that these products may be obtained by reacting a'monosubstituted cyanamide of the formula i inwhichRisanaliphaticradicalofatleast 4 n atoms chosen from the group consisting of alkyl and alkoxyalkyl radicals, or its respective dimer with a primary or a secondary alkylol amine salt, the latter being a salt of any suitable acid such as hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid, acetic acid, lactic acid, oxalic acid, citric acid, etc.

There appears to be no upper limit of carbon atoms in the substituent radical R of the monosubstituted cyanamide employed. For example,- the R may be either saturated or unsaturated, and a straight chain or a branch chain radical in which R is an aliphatic radical of at least such as isobutyl, n-amyl, sec.-amyl, n-hexyl, 2-

decyl, tetradecyl, oleyl, cetyl, octadecyL' ceryl,

montanyl, melissyl, methowpropyl, dodecyloxyethyl, oleyloxyethyl, ethyloxypropyl, 2-ethylhexoxypropyl, octadecyloxypropyl, sec.octyloxybutyl or tetradecyloxybutyl.

It is to befurther understood that the symbols R, Ra, R: and X when used hereinafter will be defined as above. i

The monosubstituted cyanamides utilized in this inventionmay be prepared-byreacting together in an inert solvent, such as beniehe or a petroleum ether fraction, the corresponding monoaliphatlc amine and a cyanogen halide according to the following equation The reaction should be carried out at relatively low temperatures to avoid further reaction between the thus formed cyanamide and amine hydrohalide. These materials are readily separated inasmuch as the amine salt is insoluble. in the reaction mixture.

I have found that the monosubstituted cyanamides' when heated polymerize readily to the re-' spective dimers as follows The following equations illustrate more fully the invention wherein a monosubstituted cyanamide is'reacted with a primary or a secondary alkylol amine salt to produce the substituted. guanidine salt, and a dimer of the monosubstituted cyanamide (e. g., a disubstituted dicyandiamide) is reacted with a primary or a secondary alkylol amine salt to produce the substituted biguanide salt:

40 parts of glacial acetic acid are added slowly with stirring to 30.5 parts of monoethylolamine. The solution is warmed to 0., and 147 parts of mono-octadecylcyanamide are added. After stirr ng and heating the mixture at l25-l30 C. for

N-n H tate.

1-eth1/lol-3-(2-dh1 lhexyl) guunidin hydrochloride a mixture consisting of 30.8 parts of mono- 2-' which 'on cooling forms a ta'n colored, wax likeproduct. This product=is -1-ethylol-3-octadecylassogaos- Exams: 8 4

. 1,1meth lat-as-ammethorvpmpul)- oiouanidc acetate 22.8 parts of mono-3-methoxypropy1cyanamide are heated at 130C. for minutes to form the dimer thereof, di-3 methoxypropyldicyandlethylhexylcyanamide and 19.6 parts of'monoethylolamine hydrochloride is stirred and heated at 125' C. forone' hour." Upon cooling, a light colored soft'waxy material obtained. l'his material is l-ethylol-3-(2-ethylhexyl) -guanidine hydrochloride. 7

, Emu 3 1 1-ethylol-3-amallmldnidi1ie' hydrochloride? 66 parts lofsmonoamylcyanamide are amide. The product is cooled to 60 0., and

a mixture consisting of 9.1 parts of diethylolamine and 12 parts of glacial acetic acid is added. :The reactionmixture is heated with stirring to 125' Cl, and thenheld at 125-130. C. for two hours. The product, L011 cooling, is a clear amher-colored viscous liquid. This product is 1,1-1

diethylol 3,5 diQ-methonpropyl) biguanide acetate. v I

The'products prepared according to this invention are of particular utility as emulsifying agents, detergents in acid solution, wetting with 48.6 'parts of :monoethylolamine hydrochloride and-the heated slowly "with stiragents, demulsiflers for breaking oil emulsions, in the formulation ofprinting inks, dye baths,

' 1 dye pastes, for depositing rubber latex emulsions ring to-l' C. After-heating for one half hour-the product is cooled to room temperature and ob tained as'a transparent'amber-colored liquid. readilysoluble in alcohol and acetone and.

sparinglysolubleg in water. This *product is '1-ethylol-3-a'mylguanidinehydrochloride.

. 1mm: 4 J 1,1 diethy'lol-3-dodecvlqiwnidi1iqacetate on cloth as flotation agents, as photographic assistants; as plasticizers, as insecticides, as

emulsifiers of resins and waxes and as softeners for leather.

parts of'glacial acetic acidare added slowly with stirring to 46 parts'oi' diethylolamine. The Y viscous liquid. readily soluble in water. This product is i,l-diethylol-S-dodecylguanadine ace- Eimnu 5 i I Q A mixture consisting of 44.6 parts of monoisopropylolamine hydrochloride and 61.6 parts of mono-2-ethylhexylcyanamide is stirred and a heated at 130 C. for one half hour, Upon cooling, a soft wax-like product is obtained. This product While the invention has been described with particular reference to specific embodiments, it

is to be understood that it is not to be limited thereto but is to be construed broadly and restricted .solely by the scope of the appended claims.

I claim: 1. The method of producing substituted biguanide salts corresponding to the formula v Bi-NRs =.N---ri B-N LN-u R-N-H in which n is an aliphatic radical r at least 7 four carbon atoms chosen from the group conslsting of alkyl and alkoxyalkyl radicals, R1 is a hydroxy-alkyl'radical, R: is a member of the group consisting of hydrogenand a hydroxyalkyl radical, and x i a salt-forming acid which is 1-propylol-3'-(2-ethylhexyl) guanidlne hydrochloride.

Exams]: 6

. 1-trimethi!lolniethul 3-amulguanidi1ie acetate for two hours at a temperature of 120-125" C.

The product, on cooling, is a clear viscous ambercolored liquid. This product is l-trimethylolmethyl-3-amylguanidine acetate.

Example: '1v 7 294 parts of mono-octadecylcyanamide are heated at 125 C. for 15 minutes to form the dimer thereof, dioctadecyldicyandiamide. 48.6 parts of monoethylolamine hydrochloride are added. and the mixture stirred and heated at 1-ethylol-3,5-dioctadeeylbiguanide hydrochloride C. for three hours. Upon cooling, 9. tancolored, wax-like product is obtained. This product is l-ethylol-3,5-dioctadecy1blguanide hydrochloride. v

comprises heating the dimer of a monosubstituted cyanamide of the formula N--CEN with an 'alkylol amine saltof the formula 7 [En] x' in which R, R1, R2, and Xare as defined above.

2. The method of producing substituted biguanide salts corresponding to the formula Iii- -H =N-H 3-11: l (1/=N'H R-N-H in which R is an aliphatic radical of at least four carbon atoms chosen from the group consisting of alkyl and alkoxyalkyl radicals, R1 is a hydroxyalkyl radical, and X is a salt-forming acid which comprises heating' the dimer of a monosubstituted cyanamide of the formula wherein R as defined above together with a primary alkylol amine salt.

3. The method of producing substituted biguam nide salts corresponding to the formula Rn-N-Rn in which R is an aliphatic radical of at least {our carbon atoms chosen from the group consisting of alkyl and aikoxyalkyl radicals, R1 is a hydroxyalkyl radical, and x is a salt-forming acid which comprises heating the dimer of a monosubstituted cyanamide oi. the formula wherein R is as defined above together with a secondary alkylol amine salt WALTER P. ERICKS. 

